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Saltville was named for the salt marshes in the area. Prior to European settlement, these marshes attracted local wildlife. Excavations at the SV-2 archaeological site in the area have recovered several well preserved skeletons of now extinct species dating back to the last ice age.[4] Indigenous peoples of varying cultures hunted at the marshes. The historic Native American people in the area were the Chisca.

Archaeologists in 1992 proposed the existence of a prehistoric "Saltville Complex Petty Chiefdom", with a paramount village located at the Northwood High School site, 44SM8. They reported "Saltville style gorgets" as well as iron and copper materials, scattered across the region.[5]

During the spring of 1567, Spanish conquistador Hernando Moyano de Morales led a force of 15-20 soldiers northward from Fort San Juan in Joara, a city in what is now western North Carolina.[6] The force attacked and burned the Chisca village of Maniatique, which may have been located at or near the site of Saltville.[7][8]

During the American Civil War, Saltville was one of the Confederacy's main saltworks. The saltworks were considered vital to the Confederate war effort because the salt was used in preserving meat for Confederate soldiers and civilians. Because of its importance, the town was attacked by Northern forces intent on destroying the saltworks. On October 2, 1864 the First Battle of Saltville was fought here. In the battle Union forces attacked Saltville but were defeated by Confederate troops. Following the battle a number of wounded black troops were murdered in what was dubbed the "Saltville Massacre." (Shortly after the war Champ Ferguson was tried, convicted, and executed for war crimes for this and other killings.)

Two months later General George Stoneman, a Union cavalry commander, led a second attack on the saltworks (known as the Second Battle of Saltville). This time the Confederates were defeated and the saltworks were destroyed by Union troops. The loss of the Saltville works was considered a major blow to the Confederacy's dwindling resources.

According to the United States Census Bureau, the town has a total area of 8.1 square miles (21.0 km²), of which, 8.1 square miles (20.8 km²) of it is land and 0.04 square miles (0.1 km²) of it (0.49%) is water.

The salt caverns in Saltville, Virginia are used for gas storage, the only one to serve the Mid-Alantic states. The cavern type in Saltville, is considered the best for this purpose because the gas can be injected and removed quickly to meet immediate demand. The structure is very safe and has the structural strength of steel.[citation needed]

Saltville was the location of the infamous "Muck Dam" break on December 24, 1924 which allowed the release of a huge volume of liquid chemical waste (stored there by the Mathieson Alkali Company) into the North Holston River taking the lives of nineteen people who lived along the river.[11] The river remained polluted and virtually dead for several decades afterward.[12][13][14][15]

Saltville is also home of the Museum of the Middle Appalachians. The museum is centrally located in the town and offers an excellent view into the past of the town and the region. The museum displays numerous exhibits on topics such as the geologic past, Civil War, the company town, and the Woodland Indians.[16]

Saltville's current mayor is C. Todd Young. Mayor Young took office in 2014 when he resoundingly defeated his opponents, garnering nearly 64% of all ballots cast.[17] The town is also regulated by a town council consisting of six other members. The current members are Randall Brickey, Darrol Coe, Johnny Norris, Ron Orr, Vincent Maiden, Terry Hunt and C. Todd Young.[18]

There were 879 households out of which 24% had children under the age of 18 living with them, 45.4% were married couples living together, 14.6% had a female householder with no husband present, and 32.5% were non-families. The average household size was 2.36 and the average family size was 2.91.

In the town the population was spread out with 24.5% under the age of 19, 6.5% from 20 to 24, 21.2% from 25 to 44, 30.5% from 45 to 64, and 17.5% who were 65 years of age or older. The median age was 43.4 years. For every 100 females there were 89.3 males. For every 100 females age 18 and over, there were 85.1 males.

The median income for a household in the town was $24,375, and the median income for a family was $42,639. Males had a median income of $36,071 versus $30,063 for females. The per capita income for the town was $19,595. About 18.1% of families and 20.6% of the population were below the poverty line, including 41.4% of those under age 18 and 15.9% of those age 65 or over.

^Barber and Barfield, "The Late Woodland in the Environs of Saltville, Virginia: A Case for Petty Chiefdom Development," 5th Upland Archaeology in the East Symposium, Boone, N.C., cited in Beck 1997 "From Joara to Chiaha"